Organic electroluminescent materials and devices

ABSTRACT

Novel substituted tetraphenylene compounds useful as host for phosphorescent emitters in OLEDs is disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 14/718,299, filed May 21, 2015, the contents of which areincorporated herein by reference.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: The Regents of the University ofMichigan, Princeton University, University of Southern California, andUniversal Display Corporation. The agreement was in effect on and beforethe date the claimed invention was made, and the claimed invention wasmade as a result of activities undertaken within the scope of theagreement.

FIELD OF THE INVENTION

The present invention relates to organic light emitting devices (OLEDs),and to organic materials used in such devices. More specifically, thepresent invention relates to novel organic materials for use as supportlayers in OLEDs, in particular as hosts and electron-blocking layermaterials, but not limited as such. The materials are based ontetraphenylene moiety. The compounds are expected to improvephosphorescent OLED performance.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting devices (OLEDs), organic phototransistors, organic photovoltaiccells, and organic photodetectors. For OLEDs, the organic materials mayhave performance advantages over conventional materials. For example,the wavelength at which an organic emissive layer emits light maygenerally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Color may be measured using CIE coordinates, which are wellknown to the art.

One example of a green emissive molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond fromnitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processible” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

SUMMARY OF THE INVENTION

According to an embodiment, a compound is disclosed, the compound havinga formula

Formula 1, wherein R¹-R⁶ are each independently selected from the groupconsisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof;

wherein at least one of R¹-R¹⁶ comprises a chemical group selected fromthe group consisting of carbazole, dibenzofuran, dibenzothiophene,dibenzoselenophene, triphenylene, fluorene, aza-carbazole,aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene,aza-triphenylene, and aza-fluorene; and

wherein the compound has the highest symmetry of C₁.

According to another embodiment, a device comprising one or more organiclight emitting devices is also provided. At least one of the one or moreorganic light emitting devices can include an anode, a cathode, and anorganic layer, disposed between the anode and the cathode, wherein theorganic layer can include a compound of Formula I including all of thevariations disclosed herein. The device can be a consumer product, anelectronic component module, an organic light-emitting device, and/or alighting panel.

According to yet another embodiment, a formulation containing thecompound of Formula I, including all of the variations, is alsoprovided.

The substituted tetraphenylene compounds disclosed herein can be used asthe host for phosphorescent emitters in organic light emitting devicesresulting in enhanced device external quantum efficiency and lifetime.Furthermore, tetraphenylene substituted with oligomeric carbazolesand/or aza-carbazoles may be used as host for phosphorescent emitters inorganic light emitting diodes.

According to some embodiments, a compound having a formula

is disclosed, wherein X¹-X¹⁶ are each independently selected from thegroup consisting of CR and N;

wherein each R is independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino, arylamino,diarylamino, carbazolyl, silyl, halosilyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof;

wherein at least one of X¹-X¹⁶ is CR;

-   -   wherein R is

-   -   wherein Y¹-Y⁸ are independently selected from the group        consisting of CR′ and N;    -   wherein each R′ is independently selected from the group        consisting of hydrogen, deuterium, halide, alkyl, haloalkyl,        cycloalkyl, heteroalkyl, arylalkyl, alkoxy, thioalkoxy, aryloxy,        thioaryloxy, amino, arylamino, diarylamino, carbazolyl,        aza-carbazolyl, silyl, halosilyl, alkenyl, cycloalkenyl,        heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,        carboxylic acids, ester, nitrile, isonitrile, sulfanyl,        sulfinyl, sulfonyl, phosphino, and combinations thereof;    -   wherein at least one of Y¹ to Y⁸ is CR′ whose R′ is a group        containing at least one carbazole or aza-carbazole.

According to some other embodiments, a device comprising one or moreorganic light emitting devices incorporating the compound of Formula 2is also provided. At least one of the one or more organic light emittingdevices can include an anode, a cathode, and an organic layer, disposedbetween the anode and the cathode, wherein the organic layer can includea compound of Formula 2 including all of the variations disclosedherein. The device can be a consumer product, an electronic componentmodule, an organic light-emitting device, and/or a lighting panel.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporatedby reference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink-jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processibility than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentinvention may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the invention canbe incorporated into a wide variety of electronic component modules (orunits) that can be incorporated into a variety of electronic products orintermediate components. Examples of such electronic products orintermediate components include display screens, lighting devices suchas discrete light source devices or lighting panels, etc. that can beutilized by the end-user product manufacturers. Such electroniccomponent modules can optionally include the driving electronics and/orpower source(s). Devices fabricated in accordance with embodiments ofthe invention can be incorporated into a wide variety of consumerproducts that have one or more of the electronic component modules (orunits) incorporated therein. Such consumer products would include anykind of products that include one or more light source(s) and/or one ormore of some type of visual displays. Some examples of such consumerproducts include flat panel displays, computer monitors, medicalmonitors, televisions, billboards, lights for interior or exteriorillumination and/or signaling, heads-up displays, fully or partiallytransparent displays, flexible displays, laser printers, telephones,cell phones, tablets, phablets, personal digital assistants (PDAs),laptop computers, digital cameras, camcorders, viewfinders,micro-displays, 3-D displays, vehicles, a large area wall, theater orstadium screen, or a sign. Various control mechanisms may be used tocontrol devices fabricated in accordance with the present invention,including passive matrix and active matrix. Many of the devices areintended for use in a temperature range comfortable to humans, such as18 degrees C. to 30 degrees C., and more preferably at room temperature(20-25 degrees C.), but could be used outside this temperature range,for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

The term “halo,” “halogen,” or “halide” as used herein includesfluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branchedchain alkyl radicals. Preferred alkyl groups are those containing fromone to fifteen carbon atoms and includes methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, thealkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals.Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms andincludes cyclopropyl, cyclopentyl, cyclohexyl, and the like.Additionally, the cycloalkyl group may be optionally substituted.

The term “alkenyl” as used herein contemplates both straight andbranched chain alkene radicals. Preferred alkenyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkenyl groupmay be optionally substituted.

The term “alkynyl” as used herein contemplates both straight andbranched chain alkyne radicals. Preferred alkynyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkynyl groupmay be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are usedinterchangeably and contemplate an alkyl group that has as a substituentan aromatic group. Additionally, the aralkyl group may be optionallysubstituted.

The term “heterocyclic group” as used herein contemplates aromatic andnon-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also meansheteroaryl. Preferred hetero-non-aromatic cyclic groups are thosecontaining 3 or 7 ring atoms which includes at least one hetero atom,and includes cyclic amines such as morpholino, piperdino, pyrrolidino,and the like, and cyclic ethers, such as tetrahydrofuran,tetrahydropyran, and the like. Additionally, the heterocyclic group maybe optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplatessingle-ring groups and polycyclic ring systems. The polycyclic rings mayhave two or more rings in which two carbons are common to two adjoiningrings (the rings are “fused”) wherein at least one of the rings isaromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl,heterocycles, and/or heteroaryls. Additionally, the aryl group may beoptionally substituted.

The term “heteroaryl” as used herein contemplates single-ringhetero-aromatic groups that may include from one to three heteroatoms,for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole,triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. Theterm heteroaryl also includes polycyclic hetero-aromatic systems havingtwo or more rings in which two atoms are common to two adjoining rings(the rings are “fused”) wherein at least one of the rings is aheteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls,aryl, heterocycles, and/or heteroaryls. Additionally, the heteroarylgroup may be optionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group,aryl, and heteroaryl may be optionally substituted with one or moresubstituents selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof.

As used herein, “substituted” indicates that a substituent other than His bonded to the relevant position, such as carbon. Thus, for example,where R¹ is mono-substituted, then one R¹ must be other than H.Similarly, where R¹ is di-substituted, then two of R¹ must be other thanH. Similarly, where R¹ is unsubstituted, R¹ is hydrogen for allavailable positions.

The “aza” designation in the fragments described herein, i.e.aza-dibenzofuran, aza-dibenzonethiophene, etc. means that one or more ofthe C—H groups in the respective fragment can be replaced by a nitrogenatom, for example, and without any limitation, azatriphenyleneencompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Oneof ordinary skill in the art can readily envision other nitrogen analogsof the aza-derivatives described above, and all such analogs areintended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described asbeing a substituent or otherwise attached to another moiety, its namemay be written as if it were a fragment (e.g. phenyl, phenylene,naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g.benzene, naphthalene, dibenzofuran). As used herein, these differentways of designating a substituent or attached fragment are considered tobe equivalent.

The inventors have found that substituted tetraphenylene compounds whenused as hosts for phosphorescent emitters in organic light emittingdevices, yields good external quantum efficiency particularly in blueand green light emitting devices. Substituents include N-carbazole anddibenzothiophene which are the key to stabilizing the charges andachieve good device lifetime. Tetraphenylene has a unique saddle-shapedstructure in which all the phenyl groups are orientated above and belowthe average plane of the molecule and have minimum conjugation. Withthis distinct structure, tetraphenylene can be envisioned as a phenylgroup and has high triplet energy. For this reason, novel substitutedtetraphenylene compounds are useful as high triplet energy hosts inorganic light emitting devices with good external quantum efficiency inthe blue and green devices.

According to an aspect of the present disclosure, a compound isdisclosed, the compound having a formula

Formula 1, wherein R¹-R¹⁶ are each independently selected from the groupconsisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof;

wherein at least one of R¹-R¹⁶ comprises a chemical group selected fromthe group consisting of carbazole, dibenzofuran, dibenzothiophene,dibenzoselenophene, triphenylene, fluorene, aza-carbazole,aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene,aza-triphenylene, and aza-fluorene; and

wherein the compound has the highest symmetry of C₁.

Tetraphenylene is a non-planar sterically cumbersome compound. Itstriplet energy by DFT calculation is 361 nm. Benzene's triplet energy bycomparison is 330 nm. The very high triplet energy of tetraphenylenesuggests there is limited electronic communication among the fourbenzene rings. Due to its high triplet energy, it is particularly usefulfor use as a building block for phosphorescence OLED hosts. Low symmetrysubstituted tetraphenylene compounds such as compounds with C₁ symmetry(mono substitution or di/tri substitution with different substituents)are especially attractive because they cannot pack well in the solidstate (such as in the thin film form in OLED) and can reduce π stackingbetween host-host molecules and host-dopant molecules, leading toreduction in luminescence quenching and improvement in luminescenceefficiency. The tetraphenylene block can therefore be viewed as a “heavybenzene,” meaning it has electronic characteristic like benzene, but themolecular weight and its steric bulk is much higher than benzene. It canbecome very useful when it is connected to more conjugated(electrochemically active) high triplet energy chromophores such ascarbazole, dibenzofuran and dibenzothopehene because the electroniccharacteristic of carbazole, dibenzofuran and dibenzothopehene will notbe much affected and their high triplet energy can be retained andbecome useful for hosting blue and green PHOLED. At the same time, sincetetraphenylene is much heavier than benzene, it can increase the glasstransition temperature (T_(g)) of thetetraphenylen-carbazole/dibenzofuran/dibenzothopehene compounds,rendering them even more suitable for OLED applications. On thecontrary, if only a benzene ring is connected tocarbazole/dibenzofuran/dibenzothopehene, the high triplet energy may beretained, but the T_(g) would be too low for OLED applications.

According to another aspect of the present disclosure, a devicecomprising one or more organic light emitting devices is disclosed. Atleast one of the one or more organic light emitting devices comprise: ananode; a cathode; and an organic layer, disposed between the anode andthe cathode. In one embodiment, the organic layer comprises a compoundhaving the formula

Formula 1, wherein R¹-R¹⁶ are each independently selected from the groupconsisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof;

wherein at least one of R¹-R¹⁶ comprises a chemical group selected fromthe group consisting of carbazole, dibenzofuran, dibenzothiophene,dibenzoselenophene, triphenylene, fluorene, aza-carbazole,aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene,aza-triphenylene, and aza-fluorene; and

wherein the compound has the highest symmetry of C₁.

In some embodiments of the compound, at least one of R¹-R¹⁶ comprises achemical group selected from the group consisting of dibenzofuran,dibenzothiophene, dibenzoselenophene, aza-dibenzofuran,aza-dibenzothiophene, and aza-dibenzoselenophene.

In other embodiments, at least one of R¹-R¹⁶ comprises a chemical groupselected from the group consisting of triphenylene, andaza-triphenylene.

In other embodiments, at least one of R¹-R¹⁶ comprises a chemical groupselected from the group consisting of dibenzofuran, dibenzothiophene,dibenzoselenophene, triphenylene, fluorene, aza-carbazole,aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene,aza-triphenylene, and aza-fluorene.

In other embodiments, at least one of R¹-R¹⁶ comprises a chemical groupselected from the group consisting of carbazole and aza-carbazole.

In other embodiments, at least two of R¹-R¹⁶ comprises a chemical groupindependently selected from the group consisting of carbazole,dibenzofuran, dibenzothiophene, dibenzoselenophene, triphenylene,fluorene, aza-carbazole, aza-dibenzofuran, aza-dibenzothiophene,aza-dibenzoselenophene, aza-triphenylene, and aza-fluorene.

In some other embodiments, at least two of R¹-R¹⁶ comprises differentchemical groups selected from the group consisting of carbazole,dibenzofuran, dibenzothiophene, dibenzoselenphene, triphenylene,fluorene, aza-carbazole, aza-dibenzofuran, aza-dibenzothiophene,aza-dibenzoselenphene, aza-triphenylene, and aza-fluorene.

In other embodiments, the compound comprises at least two differentchemical groups selected from the group consisting of carbazole,dibenzofuran, dibenzothiophene, dibenzoselenophene, triphenylene,fluorene, aza-carbazole, aza-dibenzofuran, aza-dibenzothiophene,aza-dibenzoselenophene, aza-triphenylene, and aza-fluorene.

In some embodiments, at least one of R¹-R¹⁶ is selected from the groupconsisting of carbazole, dibenzofuran, dibenzothiophene,dibenzoselenophene, triphenylene, fluorene, aza-carbazole,aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene,aza-triphenylene, and aza-fluorene.

In some embodiments, the compound is selected from the group consistingof:

According to another aspect of the present disclosure, a devicecomprising one or more organic light emitting devices is disclosed. Atleast one of the organic light emitting devices comprises an anode, acathode, and an organic layer, disposed between the anode and thecathode, wherein the organic layer comprises the compound of Formula I,including all of the variations disclosed herein.

In one embodiment of the device, the organic layer is an emissive layerand the compound is a host.

In other embodiments of the device, the organic layer can furthercomprise a phosphorescent emissive dopant.

In other embodiments of the device, the organic layer can be an emissivelayer and the compound is a host.

In another embodiment, the organic layer further comprises aphosphorescent emissive dopant. The phosphorescent emissive dopant canbe a transition metal complex having at least one ligand or part of theligand if the ligand is more than bidentate, selected from the groupconsisting of:

wherein each X¹ to X¹³ are independently selected from the groupconsisting of carbon and nitrogen;

wherein X is selected from the group consisting of BR′, NR′, PR′, O, S,Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

wherein R′ and R″ are optionally fused or joined to form a ring;

wherein each R_(a), R_(b), R_(c), and R_(d) may represent from monosubstitution to the possible maximum number of substitution, or nosubstitution;

wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independentlyselected from the group consisting of hydrogen, deuterium, halide,alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino,silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl,acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl,sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein any two adjacent substitutents of R_(a), R_(b), R_(c), and R_(d)are optionally fused or joined to form a ring or form a multidentateligand.

In another embodiment of the device, the organic layer is a chargecarrier blocking layer and the compound having Formula I is a chargecarrier blocking material in the organic layer.

In another embodiment of the device, the organic layer is a chargecarrier transporting layer and the compound having Formula I is a chargecarrier transporting material in the organic layer.

In another embodiment, the device is selected from the group consistingof a consumer product, an electronic component module, an organiclight-emitting device, and a lighting panel.

In yet another aspect of the present disclosure, a formulation thatcomprises a compound according to Formula I, and its variations asdescribed herein, is described. The formulation can include one or morecomponents selected from the group consisting of a solvent, a host, ahole injection material, hole transport material, and an electrontransport layer material, disclosed herein.

According to another aspect of the present disclosure, tetraphenylenecompounds substituted with oligomeric carbazoles and/or aza-carbazolesare potential high triplet hosts with good external quantum efficiencyin the blue emitting devices. Substituents with oligomeric carbazolesand/or aza-carbazoles are believed to stabilize the charges and achievegood device lifetime.

According to some embodiments, a compound having a formula:

is disclosed, wherein X¹-X¹⁶ are each independently selected from thegroup consisting of CR and N;

wherein each R is independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino, arylamino,diarylamino, carbazolyl, silyl, halosilyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof;

wherein at least one of X¹-X¹⁶ is CR;

wherein R is

wherein Y¹-Y⁸ are independently selected from the group consisting ofCR′ and N;

wherein each R′ is independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino, arylamino,diarylamino, carbazolyl, aza-carbazolyl, silyl, halosilyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof;

wherein at least one of Y¹ to Y⁸ is CR′ whose R′ is a group containingat least one carbazole or aza-carbazole.

In some embodiments of the compound of Formula 2, each of X¹ to X¹⁶ isCR. In some embodiments of the compound, at least one of X¹ to X¹⁶ is N.In some embodiments, each of Y¹ to Y⁸ is CR′. In some embodiments of thecompound, at least one of Y¹ to Y⁸ is N. In some embodiments of thecompound, at least one of Y¹ to Y⁸ is CR′ whose R′ is a group containingat least one carbazole. In some embodiments of the compound, at leastone of Y¹ to Y⁸ is CR′ whose R′ is a group containing at least oneaza-carbazole.

In some other embodiments of the compound, the compound of Formula 2 isselected from the group consisting of:

According to another aspect of the present disclosure, a devicecomprising one or more organic light emitting devices is disclosed. Atleast one of the organic light emitting devices comprising: an anode; acathode; and an organic layer, disposed between the anode and thecathode, comprising a compound having Formula 2:

wherein X¹-X¹⁶ are each independently selected from the group consistingof CR and N;

wherein each R is independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino, arylamino,diarylamino, carbazolyl, silyl, halosilyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof;

wherein at least one of X¹-X¹⁶ is CR;

wherein R is

-   -   wherein Y¹-Y⁸;    -   wherein Y¹ to Y⁸ are independently selected from the group        consisting of CR′ and N;    -   wherein each R′ is independently selected from the group        consisting of hydrogen, deuterium, halide, alkyl, haloalkyl,        cycloalkyl, heteroalkyl, arylalkyl, alkoxy, thioalkoxy, aryloxy,        thioaryloxy, amino, arylamino, diarylamino, carbazolyl,        aza-carbazolyl, silyl, halosilyl, alkenyl, cycloalkenyl,        heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,        carboxylic acids, ester, nitrile, isonitrile, sulfanyl,        sulfinyl, sulfonyl, phosphino, and combinations thereof;    -   wherein at least one of Y¹ to Y⁸ is CR′; and    -   wherein R′ is a group containing at least one carbazole or        aza-carbazole.

In some embodiments of the device, each of X¹-X¹⁶ is CR. In someembodiments of the device, at least one of X¹-X¹⁶ is N. In someembodiments of the device, the compound of Formula 2 is selected fromthe group consisting of Compound 470 through Compound 500.

In some embodiments of the device, the organic layer is an emissivelayer and the compound of Formula 2 is a host. In some embodiments ofthe device, the organic layer further comprises a phosphorescentemissive dopant.

In some embodiments of the device, the organic layer further comprises aphosphorescent emissive dopant, wherein the phosphorescent emissivedopant is a transition metal complex having at least one ligand or partof the ligand if the ligand is more than bidentate, selected from thegroup consisting of:

-   -   wherein each X¹ to X¹³ are independently selected from the group        consisting of carbon and nitrogen;    -   wherein X is selected from the group consisting of BR′, NR′,        PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;    -   wherein R′ and R″ are optionally fused or joined to form a ring;    -   wherein each R_(a), R_(b), R_(c), and R_(d) may represent from        mono substitution to the possible maximum number of        substitution, or no substitution;    -   wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each        independently selected from the group consisting of hydrogen,        deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,        alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,        heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,        carboxylic acids, ester, nitrile, isonitrile, sulfanyl,        sulfinyl, sulfonyl, phosphino, and combinations thereof; and    -   wherein any two adjacent substituents of R_(a), R_(b), R_(c),        and R_(d) are optionally fused or joined to form a ring or form        a multi-dentate ligand.

In some embodiments of the device, the organic layer is a charge carrierblocking layer and the compound having Formula 2 is a charge carrierblocking material in the organic layer.

In some embodiments of the device, the organic layer is a charge carriertransporting layer and the compound having Formula 2 is a charge carriertransporting material in the organic layer.

According to another aspect, a formulation comprising the compound ofFormula 2 is disclosed. The formulation can include one or morecomponents selected from the group consisting of a solvent, a host, ahole injection material, hole transport material, and an electrontransport layer material, disclosed herein

The OLED can be incorporated into one or more of a consumer product, anelectronic component module, and a lighting panel.

Combination with Other Materials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the presentinvention is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial. Examples of the material include, but are not limited to: aphthalocyanine or porphyrin derivative; an aromatic amine derivative; anindolocarbazole derivative; a polymer containing fluorohydrocarbon; apolymer with conductivity dopants; a conducting polymer, such asPEDOT/PSS; a self-assembly monomer derived from compounds such asphosphonic acid and silane derivatives; a metal oxide derivative, suchas MoO_(x); a p-type semiconducting organic compound, such as1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and across-linkable compound.

Examples of aromatic amine derivatives used in HIL or HTL include, butare not limited to the following general structures:

Each of A¹ to Ar⁹ is selected from the group consisting aromatichydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl,triphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, azulene; group consisting aromaticheterocyclic compounds such as dibenzothiophene, dibenzofuran,dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene,benzoselenophene, carbazole, indolocarbazole, pyridylindole,pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole,oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine,indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole,benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline,quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine,phenazine, phenothiazine, phenoxazine, benzofuropyridine,furodipyridine, benzothienopyridine, thienodipyridine,benzoselenophenopyridine, and selenophenodipyridine; and groupconsisting 2 to 10 cyclic structural units which are groups of the sametype or different types selected from the aromatic hydrocarbon cyclicgroup and the aromatic heterocyclic group and are bonded to each otherdirectly or via at least one of oxygen atom, nitrogen atom, sulfur atom,silicon atom, phosphorus atom, boron atom, chain structural unit and thealiphatic cyclic group. Wherein each Ar is further substituted by asubstituent selected from the group consisting of hydrogen, deuterium,halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof.

In one aspect, A¹ to Ar⁹ is independently selected from the groupconsisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH)or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not arelimited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40;(Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independentlyselected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is aninteger value from 1 to the maximum number of ligands that may beattached to the metal; and k′+k″ is the maximum number of ligands thatmay be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In anotheraspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met isselected from Ir, Pt, Os, and Zn. In a further aspect, the metal complexhas a smallest oxidation potential in solution vs. Fc⁺/Fc couple lessthan about 0.6 V.

Host:

The light emitting layer of the organic EL device of the presentinvention preferably contains at least a metal complex as light emittingmaterial, and may contain a host material using the metal complex as adopant material. Examples of the host material are not particularlylimited, and any metal complexes or organic compounds may be used aslong as the triplet energy of the host is larger than that of thedopant. While the Table below categorizes host materials as preferredfor devices that emit various colors, any host material may be used withany dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have thefollowing general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹⁰¹ is an anotherligand; k′ is an integer value from 1 to the maximum number of ligandsthat may be attached to the metal; and k′+k″ is the maximum number ofligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms Oand N.

In another aspect, Met is selected from Ir and Pt. In a further aspect,(Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the groupconsisting aromatic hydrocarbon cyclic compounds such as benzene,biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene,phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; groupconsisting aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and group consisting 2 to 10 cyclic structural units which are groups ofthe same type or different types selected from the aromatic hydrocarboncyclic group and the aromatic heterocyclic group and are bonded to eachother directly or via at least one of oxygen atom, nitrogen atom, sulfuratom, silicon atom, phosphorus atom, boron atom, chain structural unitand the aliphatic cyclic group. Wherein each group is furthersubstituted by a substituent selected from the group consisting ofhydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof.

In one aspect, host compound contains at least one of the followinggroups in the molecule:

wherein R¹⁰¹ to R¹⁰⁷ is independently selected from the group consistingof hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof, when it is aryl or heteroaryl, ithas the similar definition as Ar's mentioned above. k is an integer from0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X¹⁰¹ to X¹⁰⁸ isselected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² is selected fromNR¹⁰¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies as compared to a similar device lacking a blocking layer.Also, a blocking layer may be used to confine emission to a desiredregion of an OLED.

In one aspect, compound used in HBL contains the same molecule or thesame functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of thefollowing groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ isan integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable oftransporting electrons. Electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

In one aspect, compound used in ETL contains at least one of thefollowing groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof, when it is aryl or heteroaryl, it has the similar definition asAr's mentioned above. Ar¹ to Ar3 has the similar definition as Ar'smentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selectedfrom C (including CH) or N.

In another aspect, the metal complexes used in ETL include, but are notlimited to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinatedto atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer valuefrom 1 to the maximum number of ligands that may be attached to themetal.

In any above-mentioned compounds used in each layer of the OLED device,the hydrogen atoms can be partially or fully deuterated. Thus, anyspecifically listed substituent, such as, without limitation, methyl,phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated,and fully deuterated versions thereof. Similarly, classes ofsubstituents such as, without limitation, alkyl, aryl, cycloalkyl,heteroaryl, etc. also encompass undeuterated, partially deuterated, andfully deuterated versions thereof.

In addition to and/or in combination with the materials disclosedherein, many hole injection materials, hole transporting materials, hostmaterials, dopant materials, exciton/hole blocking layer materials,electron transporting and electron injecting materials may be used in anOLED. Non-limiting examples of the materials that may be used in an OLEDin combination with materials disclosed herein are listed in Table Abelow. Table A lists non-limiting classes of materials, non-limitingexamples of compounds for each class, and references that disclose thematerials.

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Synthesis of4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane

Tetraphenylene (10.6 g, 35.0 mmol) synthesized according to Liebigs Ann.Chem. 704, 91-108 (1967), bis(pinacolato)diboron (8.8 g, 35.0 mmol),4,4′-di-tert-butyl-2,2′-dipyridyl (1.9 g, 7.0 mmol),(1,5-cyclooctadiene)(methoxy)iridium(I) dimer (2.3 g, 3.5 mmol) andanhydrous cyclohexane (250 mL) were mixed at room temperature. Thereaction mixture was bubbled with nitrogen for 15 min. The resultantmixture was refluxed for 14 hours. The solvent was removed in vacuo. Theresidue was purified by flash column chromatography using 25%-40% of DCMin hexane (with 0.5% triethylamine). The solid obtained was then mixedwith 100 mL of MeCN and sonicated for 5 min at room temperature. Thesolid was filtered and dried under vacuum at 60° C. to afford4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane (3.2 g)as a white solid.

Synthesis of Compound 21

4,4,5,5-Tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane (1.9 g,4.5 mmol), 4-iododibenzo[b,d]thiophene (2.0 g, 6.8 mmol), K₃PO₄ (1.9 g,9.0 mmol) 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.7 g, 1.8mmol), toluene (40 mL) and water (4 mL) were mixed at room temperature.The reaction mixture was bubbled with nitrogen for 30 min. Pd₂(dba)₃(0.4 g, 0.45 mmol) was added. The mixture was bubbled with nitrogen for15 min. The resultant mixture was refluxed for 70 hours. The reactionmixture was extracted by 3 L of 50% DCM/hexane. The extract was filteredthrough a silica pad and MgSO₄. The solvent was removed in vacuo. Theresidue was purified by flash column chromatography using 10% then 15%of DCM in hexane. This product was mixed with 50 mL of heptane andbubbled with N₂ for 15 min. The resultant mixture was refluxed for 1hour. The solid was filtered and dried under vacuum at 60° C. to affordthe desired product (1.6 g) as a white solid.

Synthesis of 2-Bromotetraphenylene

4,4,5,5-Tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane (2.8 g,6.5 mmol), dioxane (150 mL), MeOH (50 mL) and CuBr₂ solution (9.1 g, 39mmol in 150 mL of H₂O) were mixed at room temperature. The reactionmixture was bubbled with nitrogen for 15 min. The resultant mixture wasrefluxed for 140 hours. The reaction mixture was extracted by 50% of DCMin hexane. The extract was filtered through a silica pad and MgSO₄. Thesolvent was removed in vacuo. The residue was purified by flash columnchromatography using 15% of DCM in hexane to afford2-bromotetraphenylene (2.2 g) as a white solid.

Synthesis of Compound 1

2-Bromotetraphenylene (3.1 g, 8.0 mmol), carbazole (8.0 g, 48.0 mmol),2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (3.3 g, 8.0 mmol),sodium tert-butoxide (3.8 g, 40.0 mmol) and toluene (100 mL) were mixedat room temperature. The reaction mixture was bubbled with nitrogen for15 min. Pd₂(dba)₃ (1.8 g, 2.0 mmol) was added. The mixture was bubbledwith nitrogen for 15 min. The resultant mixture was refluxed for 17hours. The reaction mixture was filtered through a silica pad and MgSO₄and eluted by 50% of DCM in hexane. The solvent was removed in vacuo.This product was mixed with 600 mL of MeCN and bubbled with N₂ for 30min. The resultant mixture was refluxed for 1 hour and allowed to reachroom temperature. The solid was filtered and dried under vacuum at 60°C. to afford the desired product (2.5 g) as a white solid. The tripletenergy of Compounds 1 and 21, measured at 77 K in dilute THF solutions,are 410 nm and 456 nm, respectively.

EXPERIMENTAL Experiment 1

In the OLED experiment, all device examples were fabricated by highvacuum (<10⁻⁷ Torr) thermal evaporation. The anode electrode is ˜800 Åof indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followedby 1,000 Å of Al. All devices were encapsulated with a glass lid sealedwith an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) and amoisture getter was incorporated inside the package.

Device Example 1: The organic stack of the Device Examples in Table 1consists of sequentially, from the ITO surface, 100 Å of LG101(purchased from LG Chem, Korea) as the hole injection layer (HIL), 250 Åof Compound A as the primary hole transport layer (HTL1), 300 Å ofCompound 1 doped with 20% of the emitter Compound B as the emissivelayer (EML), 50 Å of Compound C as ETL2 and 400 Å of Alq₃ as ETL1.

Device Example 2 was fabricated in the same way except as Device Example1 except that 300 Å instead of 400 Å of Alq₃ as ETL1 was used.

Device Example 3 was fabricated in the same way as Device Example 1except that 50 Å of Compound E as the secondary hole transport layer(HTL2) was inserted between the HTL 1 and EML and 300 Å, instead of 400Å, of Alq₃ as ETL1 was used.

Device Comparative Example 1 and Device Comparative Example 2 werefabricated in the same way as Device Example 1 except Compound C andCompound D were used as the host compounds in Device Comparative Example1 and Device Comparative Example 2, respectively.

The device data is summarized in Table 1 below:

TABLE 1 1931 CIE At 1,000 cd/m² Device Host Alq₃ CIE CIE λ max VoltageLE EQE PE Example HTL2 300 Å Å x y [nm] [V] [cd/A] [%] [lm/W] Devicenone Cmpd 1 400 0.175 0.393 474 5.8 52.2 23.3 28.2 Example 1 Device noneCmpd 21 300 0.170 0.373 474 5.4 47.0 21.9 27.6 Example 2 Device CmpdCmpd 21 300 0.170 0.381 474 5.4 54.7 25.1 31.8 Example 3 E (50 Å) Devicenone Cmpd D 400 0.179 0.408 474 5.8 46.5 20.3 25.2 Comparative Example 1Device none Cmpd C 400 0.178 0.406 474 5.5 47.6 20.7 27.1 ComparativeExample 2

Some of the compounds used in the devices are:

Device Example 3: The organic stack of the Device Examples in Table 2consists of sequentially, from the ITO surface, 100 Å of LG101 as thehole injection layer (HIL), 450 Å of Compound A as the hole transportlayer (HTL1), 400 Å of Compound 21 doped with 10% of the emitterCompound F as the emissive layer (EML), 50 Å of Compound Gas ETL2 and350 Å of Alq₃ as ETL1.

Device Comparative Example 3 was fabricated in the same way as DeviceExample 3 except CBP was used as the host.

The device data is summarized in Table 2.

LT80 at 20 1931 CIE At 1,000 cd/m² mA/cm² Device Host CIE CIE λmaxVoltage LE EQE PE L₀ time example 300 Å x y [nm] [V] [cd/A] [%] [lm/W][cd/m2] [h] Device Cmpd 21 0.321 0.630 523 5.9 63.2 17.6 33.6 19909 178example 3 Device CBP 0.319 0.630 522 5.1 63.6 17.7 39.5 19382 69comparative example 3

The only difference between Device Example 1 and Device ComparativeExamples 1 and 2 is the host. At 1000 cd/m², Device Example 1 withCompound 1 as the host has an efficiency of 23.3% whereas DeviceComparative Example 1 has an efficiency of 20.3% and Device ComparativeExample 2 has an efficiency of 20.7%. Compound 1 as the host is shown tobe superior to commonly used high performance hosts for bluephosphorescence OLED hosts such as Compound C and D. The increase inefficiency is presumably due to the increase of solid state tripletenergy of the host in the EML because tetraphenylene acts as asterically cumbersome block which reduces π stacking between host-hostmolecules and host-dopant molecules, particularly when thetetraphenylene compound has a low symmetry. The increase in efficiencycan also be seen in Device Example 2 with Compound 21 as the host.Although the triplet energy of Compound 21 is not as high as the tripletenergy of Compound 1, it is unexpectedly very suitable as a bluephosphorescence OLED host. The efficiency reaches 21.9%, higher than theefficiency of Device Comparative Examples 1 and 2. The efficiency can befurther enhanced when a secondary hole transport layer (Compound E) isinserted between the HTL1 and EML as demonstrated in Device Example 3. Avery high efficiency of 25.1% which is achieved.

Compound 21 was also tested as a host with a green phosphorescentemitter (Compound F). Device Example 3 with Compound 21 as the host hasan efficiency of 17.6%. On the other hand, using a standard greenphosphorescence OLED host CBP, Device Comparative Example 3 has anefficiency of 17.7%. Although the two device perform similarly, thelifetimes are very different. Device Example 3 with Compound 21 as thehost shows a much superior lifetime. LT80 (the time to reach 80% of itsinitial luminance Lo) at J=40 mA/cm² is 178 hours compared to 69 hoursof Device Comparative Example 3 with CBP as the host. The improvement is˜200%.

The device data demonstrates that OLED with tetraphenylene compoundswith low symmetry as hosts can achieve high efficiency and operationstability. In particular, due to the high triplet energy of thetetraphenylene, they are especially useful in blue and greenphosphorescence OLEDs.

Synthesis of Compound 470

An example of the inventive compound, Compound 470 was synthesized asfollows.

Synthesis of4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane

Tetraphenylene (24.3 g, 80.0 mmol), bis(pinacolato)diboron (16.3 g, 64.0mmol), 4,4′-di-tert-butyl-2,2′-dipyridyl (1.3 g, 4.8 mmol),(1,5-Cyclooctadiene)(methoxy)iridium(I) dimer (1.6 g, 2.4 mmol) andanhydrous tetrahydrofuran (1000 mL) was mixed at room temperature. Thereaction mixture was bubbled with nitrogen for 15 min. The resultantmixture was warmed at 50° C. for 3 h. The crude was filtered through asilica pad and MgSO₄ and washed with 35% DCM/hex (containing 0.5%triethylamine). The solvent was removed in vacuo and the residue waspurified by flash chromatography using 25% DCM/hexane (containing 0.5%triethylamine). The solvent was removed in vacuo and the residue wasre-crystallized by using acetonitrile to afford4,4,5,5-tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane (14.7 g,42% yield with respect to tetraphenylene) as a white solid.

Synthesis of 2-Bromotetraphenylene

4,4,5,5-Tetramethyl-2-(tetraphenylen-2-yl)-1,3,2-dioxaborolane (11.1 g,25.8 mmol), dioxane (250 mL), MeOH (80 mL) and CuBr₂(aq) (35.0 g, 150mmol, 250 mL H₂O) were mixed at room temperature. The reaction mixturewas bubbled with nitrogen for 15 min. The resultant mixture was refluxedfor 115 h. The reaction mixture was extracted by DCM. And the extractwas filtered through a silica pad and MgSO₄. The solvent was removed invacuo. The residue was purified by flash chromatography using 10%DCM/hexane to afford 2-bromotetraphenylene (9.7 g, 98% yield) as a whitesolid.

Synthesis of Compound 470

2-Bromotetraphenylene (5.3 g, 14.0 mmol), 9H-3,9′-bicarbazole (7.0 g,21.0 mmol), Pd₂(dba)₃ (1.9 g, 2.1 mmol),2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (3.5 g, 8.4 mmol),sodium tert-butoxide (2.7 g, 28.0 mmol) were added. The reaction mixturewas bubbled with nitrogen for 15 min. and refluxed for 22 h. The crudewas filtered through a silica pad and MgSO₄ and washed with 50%DCM/hexane. The solvent was removed in vacuo and the residue waspurified by flash chromatography using 20% DCM/hexane to afford Compound470 (8.0 g, 90% yield) as a white solid.

Experiment 2

In the second OLED experiment, device examples 4 and 5 were fabricatedby high vacuum (<10⁻⁷ Torr) thermal evaporation. The anode electrode is˜800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiFfollowed by 1,000 Å of Al. All devices were encapsulated with a glasslid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂Oand O₂) and a moisture getter was incorporated inside the package.

The organic stack of the Device Example 4 in Table 3 consists ofsequentially, from the ITO surface, 100 Å of LG101 (purchased from LGChem, Korea) as the hole injection layer (HIL), 250 Å of Compound A thehole transporting layer (HTL), 300 Å of Compound 470 doped with 20% ofthe emitter Compound B as the emissive layer (EML), 50 Å of Compound Cas ETL2 and 300 Å of Alq₃ as ETL1. Device Example 5 was fabricated inthe same way except the emitter in Device Example 5 was Compound Hinstead of Compound B.

TABLE 3 Summary of data from EXPERIMENT 2 At 1,000 cd/m² At 20 mA/cm²1931 CIE Em_(max) Voltage LE EQE PE L₀ LT_(80%) Device Host x y [nm] [V][cd/A] [%] [lm/W] [cd/m²] [h] Example 4 Cmpd 0.170 0.374 474 5.1 50.422.9 30.8 8118 40 470 Example 5 Cmpd 0.147 0.225 462 5.0 18.5 11.5 11.73374 8 470

The data in Table 3 shows that Compound 470 can be an excellent host interms of device efficiency and lifetime. Device Example 4 shows thatCompound 470 can host Compound B (sky blue emitter) with excellentexternal quantum efficiency of 22.9% and LT_(80%) of 40 hrs at J=20mA/cm². Device Example 5 shows that Compound 470 can host Compound D(deep blue emitter) with decent external quantum efficiency of 11.5% andLT_(80%) of 8 hrs at J=20 mA/cm². The excellent efficiency may be due tothe higher triplet energy of Compound 470. In addition, thenon-planarity of the tetraphenylene ring may decrease molecular packingin the solid state and decrease the solid state triplet and improvemixing of the dopant in the host:dopant matrix.

We claim:
 1. A compound having a formula:

wherein X¹-X¹⁶ are each independently selected from the group consistingof CR and N; wherein each R is independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino,arylamino, diarylamino, carbazolyl, silyl, halosilyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; wherein at least one ofX¹-X¹⁶ is CR; wherein R

wherein Y¹-Y⁸ are independently selected from the group consisting ofCR′ and N; wherein each R′ is independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino,arylamino, diarylamino, carbazolyl, aza-carbazolyl, silyl, halosilyl,alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl,carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl,sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein atleast one of Y¹ to Y⁸ is CR′ whose R′ is a group containing at least onecarbazole or aza-carbazole.
 2. The compound of claim 1, wherein each ofX¹ to X¹⁶ is CR.
 3. The compound of claim 1, wherein at least one of X¹to X¹⁶ is N.
 4. The compound of claim 1, wherein each of Y¹ to Y⁸ isCR′.
 5. The compound of claim 1, wherein at least one of Y¹ to Y⁸ is N.6. The compound of claim 1, wherein at least one of Y¹ to Y⁸ is CR′whose R′ is a group containing at least one carbazole.
 7. The compoundof claim 1, wherein at least one of Y¹ to Y⁸ is CR′ whose R′ is a groupcontaining at least one aza-carbazole.
 8. The compound of claim 1,wherein the compound of Formula 2 is selected from the group consistingof:


9. A device comprising one or more organic light emitting devices, atleast one of the organic light emitting devices comprising: an anode; acathode; and an organic layer, disposed between the anode and thecathode, comprising a compound having a formula:

wherein X¹-X¹⁶ are each independently selected from the group consistingof CR and N; wherein each R is independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, haloalkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino,arylamino, diarylamino, carbazolyl, silyl, halosilyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; wherein at least one ofX¹-X¹⁶ is CR; wherein R is

wherein Y¹-Y⁸; wherein Y¹ to Y⁸ are independently selected from thegroup consisting of CR′ and N; wherein each R′ is independently selectedfrom the group consisting of hydrogen, deuterium, halide, alkyl,haloalkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, thioalkoxy,aryloxy, thioaryloxy, amino, arylamino, diarylamino, carbazolyl,aza-carbazolyl, silyl, halosilyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; wherein at least one of Y¹ to Y⁸ is CR′; andwherein R′ is a group containing at least one carbazole oraza-carbazole.
 10. The device of claim 9, wherein each of X¹-X¹⁶ is CR.11. The device of claim 9, wherein at least one of X¹-X¹⁶ is N.
 12. Thedevice of claim 9, wherein the compound of Formula 2 is selected fromthe group consisting of:


13. The device of claim 9, wherein the organic layer is an emissivelayer and the compound is a host.
 14. The device of claim 9, wherein theorganic layer further comprises a phosphorescent emissive dopant. 15.The device of claim 9, wherein the organic layer further comprises aphosphorescent emissive dopant, wherein the phosphorescent emissivedopant is a transition metal complex having at least one ligand or partof the ligand if the ligand is more than bidentate, selected from thegroup consisting of:

wherein each X¹ to X¹³ are independently selected from the groupconsisting of carbon and nitrogen; wherein X is selected from the groupconsisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, andGeR′R″; wherein R′ and R″ are optionally fused or joined to form a ring;wherein each R_(a), R_(b), R_(c), and R_(d) may represent from monosubstitution to the possible maximum number of substitution, or nosubstitution; wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are eachindependently selected from the group consisting of hydrogen, deuterium,halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and wherein any two adjacent substituents of R_(a), R_(b),R_(c), and R_(d) are optionally fused or joined to form a ring or form amulti-dentate ligand.
 16. The device of claim 9, wherein the organiclayer is a charge carrier blocking layer and the compound having FormulaI is a charge carrier blocking material in the organic layer.
 17. Thedevice of claim 9, wherein the organic layer is a charge carriertransporting layer and the compound having Formula 2 is a charge carriertransporting material in the organic layer.
 18. The device of claim 9,wherein the device is selected from the group consisting of a consumerproduct, an electronic component module, and a lighting panel.
 19. Aformulation comprising the compound in claim 1.